TW200535005A - Bonding of dynamic vulcanizates of fluorocarbon elastomers - Google Patents

Abstract

A method of enhancing the adhesion of a thermoplastic fluoroelastomer composition to a substrate, and for making composite articles, involves applying a partially cured dynamic vulcanizate of a fluoroelastomer and a thermoplastic material onto a substrate, and curing the partially cured dynamic vulcanizate while it is in contact with the substrate. The partially cured dynamic vulcanizate is made by dynamically vulcanizing a fluoroelastomer in the presence of a thermoplastic and a curing agent under conditions of time and temperature such that the fluoroelastomer is less than completely cured. The cure is completed when the dynamic vulcanizate is in contact with the substrate.

Description

200535005 IX. Description of the invention: [Technical Field of the Invention] 3 Introduction This invention relates to a fluoropolymer composition and its adhesion to polymers and other 5 substrates. The present invention further relates to a composite article containing a fluoropolymer bonded to a substrate. Fluorinated polymers possess uniquely combined favorable physical properties. For example, polymers are generally characterized by high stability and resistance to a wide variety of different chemical fluids 10. These properties make the polymer valuable for applications where the material is in contact with a fluid, such as a seal. The fluorocarbon rubber is an elastomer material made of a copolymer of a fluorine-containing monomer. In addition to the stability and fluid resistance of general fluoropolymers, cured rubbers have elastomeric properties typical of rubber materials. Fluorocarbon 15 rubber is widely used in seals and joint gaskets. In some applications, 'fluorocarbon rubber can be molded into objects that act directly as seals (such as' 0-rings') and gaskets. For other applications, it is desirable to provide composite articles containing fluorocarbon rubber components and substrates. The substrate improves physical strength and enables carbon-gas compound elastomers to be incorporated into a wider variety of different structures used in dense 20 seals and other applications. However, the bonding of the 'fluorocarbon rubber material with metals and other substrates (such as HH and other elastomers) is difficult to achieve because of the low surface energy state of materials with a molecular structure. Bonding can be promoted by <, anaerobic polymer and substrate mechanical interlocking structure. Bonding of fluorocarbon 200535005 compound elastomers can also be achieved by coupling molecule reactions in the adhesive layer during the curing process. These can cause or trigger chemical reactions between the fluorinated elastomer and the coupling agent molecules. Dynamic vulcanizates of fluorocarbon elastomers are composed of solidified fluorocarbon elastomer particles in a discontinuous phase in a thermoplastic material such as a fluoroplastic. The fully cured nature of the fluoroelastomer particles means that dynamic vulcanized rubber cannot trigger chemical reactions between the elastomer molecules and the coupling agent molecules used in traditional fluoroelastomer adhesives. In addition, because the continuous matrix is made of a thermoplastic material such as fluoroplastic, the cured elastomer particles are not in close contact with the surface of the substrate to which it is bonded. It is desired to provide adhesion between dynamically vulcanized rubber and metal and other substrates that promote fluorocarbon elastomers. In addition, it is desired to provide a method for manufacturing a composite object in which a fluoroelastomer dynamic vulcanized rubber is adhered to a substrate. Mingner 1] 15 Summary The present invention provides a method for promoting adhesion between a thermoplastic fluoroelastomer composition and a substrate and manufacturing a composite article. In various embodiments, these methods include applying a partially cured dynamic vulcanizate and thermoplastic material of a fluoroelastomer to a substrate, and curing the partially cured dynamic dredging rubber upon contact with the substrate. This partially cured material is applied by bringing it into contact with the substrate in a variety of different methods, such as prayer, post-entry molding, and co-extrusion. Partially cured dynamic vulcanized rubber is preferably obtained by dynamically vulcanizing the aeroelastomer in the presence of a thermoplastic material and a curing agent under conditions such that the aeroelastomer is fully cured. The curing is complete when the dynamic vulcanized rubber 200535005 adhesive comes into contact with the substrate. In various embodiments, the substrate includes an adhesive or an adhesive layer in contact with the solid building. In this embodiment, the partially cured thermoplastic elastomer elastomer la is in contact with the spotting agent layer. [Implementing the cold type] 5 Detailed description The following meanings and non-limiting criteria need to be considered when reviewing the description of the invention described herein. The headers used here (such as ,, preamble, and "summary") are only intended to generalize the headings in the disclosure order of the present invention, and are not intended to limit the content of the disclosure disclosed in this publication or In any respect, in particular, the subject matter disclosed in the preamble may include all technical aspects within the scope of the Maoming and does not constitute the subject matter disclosed in the description of the conventional art. A thorough or complete disclosure of any embodiment. The references cited herein do not constitute an admission that these references are known in the art or are patentable in any way related to the invention disclosed herein. All references cited in the detailed description section of the specification References are hereby incorporated in their entirety. Descriptions and special embodiments of Putian, while indicating preferred embodiments of the present invention, are intended to be illustrative and not intended to limit the scope of the present invention. 20 Furthermore, it has the stated features. The description of several embodiments is not intended to exclude other embodiments having additional features, or to incorporate differences or combinations of the features described: Examples. Special embodiments are provided for use as examples. How to make the composition and method of the invention ^ application ^ invention, and unless specifically stated otherwise, it is intended to represent that a particular embodiment of the invention has been or has not been manufactured ^ 200535005. When used herein, "preferred" and Terms such as "preferably" refer to embodiments of the invention that provide certain benefits under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, one or more of the The description of the preferred embodiment 5 does not imply that other embodiments are useless, and it is not intended to exclude other embodiments from the scope of the present invention. As used herein, the word "including" and its variations are intended to be non-limiting, The description of such enumerated items does not exclude other similar items of materials, compositions, devices, and methods that can also be used in the present invention. 10 In one aspect, the present invention provides a method for adhering a thermoplastic fluoroelastomer composition to a solid substrate This method includes a method for adhering a thermoplastic elastomer composition to a solid substrate, including: (a) Dynamically curing a fluoroelastomer continuously in the presence of a thermoplastic material and a curing agent The fluoroelastomer is fully cured in less time, forming part 15 cured thermoplastic vulcanizate, (b) applying an adhesive layer to the substrate, (C) curing the partially cured thermoplastic vulcanizate with the adhesion Contact with the agent layer; and (d) complete curing of the thermoplastic vulcanizate. 20 The dynamic curing of the fluoroelastomer in the presence of the fluorinated thermoplastic material and the curing agent is less than the time required to completely cure the fluoroelastomer at the temperature used. In this way, a partially cured thermoplastic dynamic vulcanizate is formed. In a separate step, the adhesive layer is applied to a substrate such as metal, plastic, ceramic, or another elastomer. The partially cured thermoplastic vulcanizate and adhesive The adhesive layer is in contact with 200535005, and the thermoplastic vulcanizate is completely cured when it is bonded. The vulcanized rubber is contacted with the adhesive layer by various methods, such as molding, and co-extrusion. In various embodiments, the elements of this method include: «Partially cured thermoplastic vulcanizate is insert-molded onto the adhesive-coated substrate. (When referred to here, "method elements" refer to the steps or other activities performed in this method. Unless otherwise specified or required by the content of the method elements, these elements can be implemented sequentially or simultaneously.) In the embodiment, the adhesive layer is co-extruded between the partially cured thermoplastic vulcanizate and the substrate. In one embodiment, the adhesive layer is applied during 10 extrusions with the liquid continuous injection unit. Fluorocarbon elastomer Copolymers containing one or more fluorine-containing monomers such as vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene, and perfluorovinyl ether. Fluorocarbon elastomers may additionally contain a curing site monomer. Conventional use Curing agents for fluorocarbon elastomers can be used, such as bisphenol curing agents and 15 epoxide curing agents. On the other hand, a method of manufacturing a composite article is provided. The composite article includes an adhesive A solid substrate of a cured fluoroelastomer composition. These methods include those used in the manufacture of composite articles that include: (a) coating a partially cured thermoplastic elastomer composition To the substrate, 20 wherein the thermoplastic elastomer composition comprises a partially cured fluoroelastomer and a continuous phase thermoplastic polymer material; and (b) the partially cured thermoplastic elastomer composition Curing. In the preferred embodiment, partially cured fluoroelastomer and thermoplastic vulcanizates are applied to the substrate, and the partially cured vulcanized rubber 200535005 is completely cured when in contact with the substrate. Department The partially cured dynamic vulcanized rubber tire is a thermoplastic polymer material that contains partially cured fluoroelastomer particles with a discontinuous phase and a continuous phase. The partially cured dynamic vulcanized rubber is aeroelastically heated by the presence of & thermoplastic material. When the body part is cured, the aeroelastic 5 body, the thermoplastic material and the curing agent are mixed together. The thermoplastic material may be a fluoroplastic material or a non-fluorine-containing thermoplastic polymer. The aeroelastic body optionally includes a curing position monomer, And curing agents such as bisphenol or epoxide. Various embodiments in which the substrate includes an adhesive layer, the adhesive layer is applied to the solid support 'And the partially cured dynamic vulcanizate is applied to the adhesive layer 10. The partially cured material is applied to the substrate by various methods including insert molding and coextrusion. In coextrusion In the method, a partially cured dynamic vulcanized rubber is prepared, which includes a partially cured discontinuous phase of a fluoroelastomer and a continuous phase containing a thermoplastic polymer material. The partially cured dynamic vulcanized rubber and a substrate are co-extruded to provide 15 Contact. Further curing of the partially cured dynamic vulcanized rubber is performed after co-extrusion and when these layers are in contact. Optionally, the adhesive layer is co-extruded between the dynamic vulcanized rubber and the substrate layer. In various embodiments, Partially cured dynamic vulcanizates are prepared by mixing together a fluoroelastomer resin, a thermoplastic polymer material, and a curing agent capable of reacting with the fluoroelastomer resin 20. The mixture is heated during mixing to cause the fluoroelastomer resin Reacts with curing agents. The reaction takes less time than required to fully cure the resin. For example, mixing a thermoelastomer and a thermoplastic material together is generally performed for a time corresponding to T90 or less, where T90 is a traditional parameter related to the curing of the elastomeric material. 200535005 yv and Gan Ruren; various methods of manufacturing, the adhesive layer is coated on the substrate, and then the substrate covered with the adhesive is placed in the mold. After that, a partially cured elastomer composition (such as the dynamic vulcanizate described above) is embedded in the mold to contact the substrate. Then, the elastomer composition keeps the disc substrate 5 in contact until the curing of the elastomer is complete—a further step. Dynamic vulcanization or mixing of fluoroelastomers and thermoplastic materials is performed by batch, continuous, or semi-batch technology. In one method, a mixture of uncured carbon iU compound elastomer and thermoplastic material can be fed into the sleeve of a twin screw dispenser. The fed mixture is blended in a sleeve 10 of a twin-screw extruder and heated until it reaches a downstream hole for feeding the curing agent into the mixture. Further mixing of the curing agent, the fluorocarbon elastomer, and the thermoplastic material in the sleeve of the extruder takes less time than required to fully cure the fluoroelastomer, for example, T90 or less. Before the fluoroelastomer is completely cured, the partially cured thermoplastic vulcanizate is extruded from the sleeve. Thereafter, a vulcanized rubber was applied to the substrate. The curing of the vulcanized rubber is complete upon contact with the substrate. The partially cured thermoplastic vulcanizates in various embodiments' were either directly injected into a co-extrusion mold or immediately embedded in a mold containing a substrate as discussed above. In addition, the extruded vulcanizate is cooled and maintained for subsequent use. A processable rubber composition is provided that includes a vulcanized elastomer material dispersed in a matrix rain. The vulcanized elastomer material is the product of vulcanizing, crosslinking, or curing carbon compound elastomers. The matrix is made of a thermoplastic material. The processable rubber composition is processed by various methods. 200535005 includes traditional thermoplastic technology to form a composite object with a rubber composition attached to a solid substrate. The rubber composition of the composite article has physical properties that make it useful in several applications requiring elastomeric properties. In particularly preferred embodiments, the rubber composition exhibits a Shore A hardness of about 50 or more, a Shore a of 5 or more, or a range of about Shore A 70 to about Shore A 90. In addition or in addition, the tensile strength is preferably about 4 MPa or more, about 8 MPa or more, or about 8 to about 13 MPa. In other embodiments, the cured rubber is characterized by having a 100% modulus of at least 2 MPa, or at least about 4 MPa, or about 4 to about 8 MPa. In other embodiments, the 10 elongation at break of an article made from the processable composition of the present invention is 10% or more, preferably at least about 50%, or at least about 150%, or about 150 to about 300 %. The molded article of the present invention is preferably characterized by having at least one of hardness, tensile strength, modulus, and elongation at break in the ranges shown above. In one aspect, the rubber composition is made of two phases, wherein the matrix is formed into a continuous phase, and the hardened elastomeric material is in the form of particles that form discontinuous, dispersed or separate phases. On the other hand, the elastomer material bamboo and matrix form a common continuous phase. In a preferred embodiment, the composition contains about 35% by weight or more, or about 40% by weight or more of the elastomer phase, which is based on the total weight of the elastomer and the thermoplastic material 20. In other embodiments, the composition contains about 50% by weight or more of a heterogeneous phase. The composition is a homogeneous f blend of two phases, which is fully compatible so that the composition can be easily formed, and has sufficient elastomer properties (such as tensile strength, modulus, fracture extension, and compression set) for molding Objects are therefore used in the industry for applications that require elastomeric properties, such as dense 12 200535005 seals, hoses, etc. The elastomer phase can be in the form of particles in the continuous thermoplastic phase and form a 3D network of common continuous phases with surface plastic materials. Therefore, one ..., °, or a mixture of them. The particles of the elastomer phase or the 3-D network are preferably "10 μηι or less, or a small size of about 1 μιη or less. In various embodiments, the rubber composition of the present invention is made of plastic. It is prepared by dynamically vulcanizing a fluorine-breaking compound elastomer in the presence of components. In this embodiment, a method for manufacturing a rubber composition is provided. The pot contains a curing agent, an elastomer material, and a thermoplastic material to form a mixture. The mixture is 10 -Temperature heating and continuous presence of Ashizaki thermoplastic material causes vulcanization or curing of the carbon gas elastomer part, but is performed for less time than required for full curing. Mechanical energy is applied during the heating step To the mixture of elastomer material, curing agent and thermoplastic material. Therefore, the method of the present invention provides mixing of elastomer and thermoplastic components in the presence of curing agent 15 and heating during mixing to produce partial curing of the elastomer component. In addition, elasticity The bulk and thermoplastic materials are mixed at a shear rate sufficient to form a dispersion of the elastomeric material in a continuous or co-continuous thermoplastic phase. A period of time. Thereafter, the curing agent is a dispersion added to the elastomeric material and the thermoplastic material while the mixing is continued. Finally, the dispersion is heated while the mixing is continued to produce a processed rubber composition of the present invention. In the embodiment, the composite object made from the composition of the present invention exhibits a favorable combination of physical properties, including a high resistance to the effects of chemical solvents. In a preferred embodiment, the object is made when the object is exposed for a long time , Such as, secondary or partial immersion in organic solvents or fuels, with little change in hardness, resistance to 13 200535005 tensile strength and / or elongation at break, or comparable cured fluorocarbon elastomers or other Compared with thermoplastic vulcanizates, the change is significantly less. Preferred fluorocarbon elastomers contain one or more fluoromonomers (such as' vinylidene fluoride (VDF), hexafluoropropylene (HFP), tetrafluoro Commercially available copolymers of ethylene (tfe) and permoethylene vinyl scale (PFVE). The preferred pfve contains those with a Cw perfluoroalkyl group, preferably a perfluoroalkyl group with 1 to 6 carbons, And especially perfluoromethyl Vinyl ether and perfluoropropyl vinyl ether. Furthermore, the selectivity based copolymer comprising from such as ethylene (Et) and propylene (Pr) of the olefin-derived

10 repeating units. Copolymers may also contain relatively small amounts of curing site monomers (CSM), which are discussed further below. Preferred copolymer fluorocarbon elastomers include VDF / HFP, VDF / HFP / CSM, VDF / HFP / TFE, VDF / HFP / TFE / CSM, VDF / PFVE / TFE / CSM, TFE / Pr, TFE / Pr / VDF, TFE / Et / PFVE / VDF / CSM, TFE / Et / PFVE / CSM 15 and TFE / pFVE / CSM. The elastomer designation refers to a single body of synthetic elastomer glue. Elastomer glue preferably has a viscosity of about 15 to about (ML1 + 10, large rotor, at about 121. Mooney viscosity, which can be selected for the mixing of flow and physical properties. Elasticity Bulk suppliers include Dyneon (3M), Asahi Glass Fluoropolymers, Solvay / Ausimont, 20 Dupont, and Daikin. In one embodiment, the elastomer material is described as a copolymer of tetrafluoroethylene and at least one C2. 4 olefin. Therefore, Elastomer materials include repeating units derived from tetrafluoroethylene and at least one C2_4 olefin. Alternatively, the elastomeric material may contain repeating units derived from one or more additional fluoromonomers. 14 200535005 Vulcanized elastomer Among the preferred materials are monovinylidene fluoride. Other fluoromonomers that are selectively used in elastomer materials include perfluoroalkyl vinyl compounds, perfluoroalkyl vinylidene compounds, and perfluoroalkanes. Oxyvinyl compounds. Examples of hexafluoropropylene (HFP) based perfluoroalkyl vinyl monomers. Examples of perfluorofluorovinyl ethers are preferred perfluoroalkoxy vinyl monomers. For example, Teflon Rubber based on copolymers of ethylene and perfluoromethyl vinyl ether are commercially available from Dupont under the trade name of Viton® ETP. In another embodiment, the elastomer material contains self-vinylidene fluoride (VDF ) And hexafluoropropylene (HFP) fluoromonomer-derived repeating units of curable carbon 10 fluorine compound elastomers. In some embodiments, the elastomers further contain repeating units derived from tetrafluoroethylene. Chemically, In this embodiment, the elastomer material is made of a copolymer of VDF and HFP or a terpolymer of VDF'HFP and tetrafluoroethylene (TFE) and a selective curing site monomer. In a preferred embodiment, it Contains about 66 to about 15 70% by weight of fluorine. Elastic systems are commercially available and examples are DuPond Dow

Elastomers' Viton® A, Viton® B, and Viton® F series elastomers. Grades containing gum polymers alone or as pre-compounds containing curing agents are commercially available. In another embodiment, the elastomer is chemically described as tFE & pfve, which is a ternary polymer with VDF selectivity. The elastomer may further contain repeating units derived from the monomer at the curing site. In various embodiments, the fluorochemical elastomer material used to make the processable rubber of the present invention is formed by free radical emulsification of a monomer mixture containing a starting monomer in a desired mole ratio. Prepared by polymerization. Since 15 200535005 The initiator contains organic or inorganic peroxide compounds, combined emulsifier packs, and acid soaps. In the-examples, the molecular weight of the polymer formed is controlled by the choice of the relative amount of initiator used and the transfer agent (if any) as compared to the early body. Suitable transfer agents include carbon tetrachloride, methanol and lysine. Emulsion polymerization is carried out under the conditions τ. Scale systems can be purchased as shown above. --- Carbon gas elastomers may also contain up to about 5 mol% and preferably up to about 3 mol% from the so-called curing site monomer (which provides curing sites for vulcanization as described below) Derived repeating units. In one embodiment, the 10-curing-position repeating unit is derived from a olefin-containing monomer and / or a magnetic-containing monomer. If used, preferably, the repeating units of the iodine- or bromine-containing monomer are present in an amount that provides at least about 0.05% of the polymer in the polymer, preferably 0-3% or more. . In a preferred embodiment, the total weight of bromine or iodine in the polymer is about 1.5% by weight or less. 15 A bromine-containing olefin single system for providing a curing position for a fluoropolymer is disclosed, for example, in U.S. Patent No. 4,035,565. Non-limiting examples of bromine-containing monomers include monobromotrifluoroacetamidine and 4-bromo-3,3,4,4-tetrafluoro-1-butene. Additional non-limiting examples include ethylene bromide, 1-bromo_2,2-difluoroacetamidine, perfluoroalkyl bromide, 4-bromo-fluorene, i, 2-trifluorobutene, 4-bromo- 1,1,3,3,4,4-Hexafluorobutane, 2-bromo 4-bromo-3_gas-1,1,3,4,4, -pentafluorofluorobutene, 6-mo, -5, 5,6,6-tetramethylhexene, 4-bromoperfluorobutene, and 3,3-difluoroallyl bromide. As indicated above, it is generally preferred that sufficient bromo-olefin repeating units are present in the copolymer to provide about 0.3-1.5% by weight of the copolymer. Other curing monomers can be used, which introduce low levels (preferably less than or equal to 16 200535005 equal to about 5 mole%, and more preferably less than or equal to about 3 mole%) such as epoxy, anti-acid, Wei Functional groups of acid halides, chitosan acid, acid salts, luteinic acid, phenylalanine, and sodium phosphate. Such monomers and curing are described, for example, in U.S. Patent No. 5,354,811 by Kamiya et al. 5 The thermoplastic resin that touches this substrate is a polymer material that softens and flows when heated. On the other hand, thermoplastic materials are those whose melt viscosity can be measured at temperatures above their melting point (such as by ASTM238 or D_2u6). The thermoplastic material of the present invention can be selected so that at elevated temperatures, it is preferred that Π) be above the agreement. C and more preferably at about 15 ° C and higher, providing the promoting properties of the rubber / thermoplastic material mixture. These thermoplastic materials include physical properties such as tensile strength, modulus, and elongation at break at elevated temperatures In the preferred embodiment, the thermoplastic material possesses better physical properties at elevated temperatures than comparable cured carbon gas elastomers (rubbers) at comparable temperatures (ie, Higher tensile strength, higher modulus, and / or higher elongation at break). In various embodiments, the thermoplastic polymer material is a thermoplastic elastomer. Thermoplastic elastomers have certain physical properties of rubber, such as , Softness, flexibility and elasticity, but can be processed like a thermoplastic material. The composition that is transferred from the melt to 20 and transformed into a solid and evil rubber-like composition occurs quite quickly when cooling. This is contrary to traditional elastomers. It hardens slowly when heated. The thermoplastic elastomer system in various embodiments is processed on conventional plastic processing equipment, such as' injection molding machines and extruders. The debris is preferably easily recycled. Heat The elastic elastomer has a multi-phase structure, in which these phases are generally related to 17 200535005 mountain D. Yu Xujiao 'This #phase storage is polymerized by grafting or nucleus, heart: maintained at-from. At least-phase Because it is hard at room temperature, but heating # is the material of the body is made of a softer material that is rubbery at room temperature.

5 Many thermoplastic elastomer systems are known to users here. Secret examples of ABA type = plastic elastomers include polystyrene ethoxylate / polystyrene, polystyrene / polyethylene-co-butadiene / polystyrene, polystyrene / polybutadiene polybenzene Ethylene, polystyrene / polyisoprene / polystyrene, poly_α_methylstyrene / polybutadiene / polymethylstyrene, poly-ex-methylstyrene / 10 polyisoprene Diene / poly · α-methylstyrene, and polyethylene / polyethylene co-butylene polyethylene. Non-limiting examples of thermoplastic elastomers with (A-B) η repeating structures include polyammonium / fluorene, polyamines / polydimethylene sulfide, polyurethane / water® Vinegar / poly shout, poly vinegar / poly shout, polycarbonate / polydimethyl 15-based stone burner, and polyhexyl ester / polyether. In the embodiment, the thermoplastic elastomer has alternating polyamines and polyethers. These materials include what can be said, for example, the trade name of Atofina. The polyfluorene segment can be derived from a copolymer of a diacid component and a diamine component, or can be prepared by the homopolymerization of a cyclic lactam. The polyblocks 20 are generally homopolymers or copolymers that touch the ring, such as ethylene oxide, propylene oxide, and tetrachloromethane. In the embodiment, the thermoplastic polymer material is a plastic material selected from the solid-state polymer S generally. Preferably, the material is a crystalline or semi-crystalline polymer ' and more preferably has a degree of crystallinity of at least about 25%, which is determined by differential scanning. Non-crystalline polymers with suitably high glass transition temperatures are also suitable as thermoplastic polymer materials. The thermoplastic material preferably also has a dry melting temperature or glass transition temperature of about 80 C to about 350 C, but the melting temperature is generally lower than the decomposition temperature of Newaywei. " 5 Non-limiting Examples of Thermoplastic Polymers + Polyolefins, Polyglycans, Nonyl, Polycarbonate S, Copolymers of Styrene and Acrylonitrile, Polyethylene Terephthalate, Polyisocyanate Butylene diphthalate, polyamine, polystyrene, polyethylene derivatives, polyethylene oxide, polyphenylene oxide, polyoxymethylene, and gas-containing thermoplastic materials. 10 Polyolefins are produced by polymerizing a-olefins (such as ethylene, propylene, hene, 1-hexene, 1-octane, 2-methyl-r propylene, 3. Limonene, 5-methyl-1.hexene, and mixtures thereof, but are not limited thereto). Ethylene and propylene or propylene or propylene with another α-olefin (such as 丨 _butene, 1-hexene, 1-octene, 2-methyl-1-propylene, 3_methyl_ 丨 _pentene, 4 (Methyl 15-pinene, 5-fluorenyl hexene, or a mixture thereof) can also be considered. These equivalent polymers and copolymers, and the like, can be combined as the thermoplastic polymer material of the present invention. ^ Polyacetate thermoplastics contain repeating ester-linking units in the polymer backbone. In one embodiment, they contain repeating units derived from a low molecular weight diol and a low molecular = 20 aromatic diacid. Non-limiting examples include polyethylene terephthalate and polybutylene terephthalate, which are available in grades. In addition, the purpose of the polysaccharides can be known as monohydric alcohols and monocarboxylic acids. An example is a copolymer of ethylene glycol and adipic acid. In another embodiment, the thermoplastic polyacetate is a polymer duck prepared by polymerizing monomers containing a vial and a tertiary functional group. 19 200535005 Caprolactone is one non-limiting example of such a thermoplastic polyester. Polyamide thermoplastics contain fluorene linkages to the polymer backbone. In one embodiment, polyamines contain repeating units derived from diamine and diacid monomers, such as known polymers of nylon 66, hexamethylenediamine, and adipic acid. Its 5K resistant Fen has a structure formed by changing the size of the diamine and diacid components. Non-limiting examples include Nylon 610, Nylon 612, Nylon, and Nylon 6/66 copolymer. In another embodiment, the polyamidoamine has a structure formed by polymerizing a monomer having an amine and a carboxylic acid moiety. Non-limiting examples include nylon 6 (polycaprolactam), nylon 11, and nylon 12. 10 Other polyamines made from diamine and diacid components include high temperature aromatic polyamines containing repeating units derived from diamines and aromatic diacids such as terephthalic acid. These commercially available examples include PA6T (copolymer of hexamethylene diamine and terephthalic acid), and PA9T (copolymer of hexamethylene diamine and terephthalic acid), which are sold by Kuraray under the Genestar trade name. For some applications, 15 some aromatic polyamides have higher melting points than the best for thermoplastic processing. In these cases, the melting point is lowered by making a suitable copolymer. By way of non-limiting example, in the case of PA6T, which has a melting point of about 370 ° C, the melting point can actually be achieved by including an effective amount of a non-aromatic diacid (such as adipic acid) in the manufacture of the polymer. Drop to a moldable 20 temperature below about 32 ° C. In another preferred embodiment, a copolymer of an aromatic diacid (such as terephthalic acid) and a diamine containing more than 6 carbon atoms (preferably containing 9 or more atoms) is mainly used. Aromatic polyamines are used. The upper limit of the carbon chain length of the diamine is, from a practical point of view, limited to the appropriate availability of suitable monomers for polymer synthesis. Suitable diamines include those having 7 to 20 carbon atoms (preferably in the range of 9 to 15 carbons, and more preferably in the range of 9 to 12 carbons). The preferred embodiment comprises aromatic polyfluorene amines mainly composed of diamines of C9, C10 and C11. Preferably, these aromatic polyamidoamines exhibit increased solvent resistance, primarily based on the lipophilic nature of carbon chains with more than 6 5 carbons. If the melting point is to be lower than the car's good molding temperature (typically about 32 ° C or lower), the aromatic polyamines mainly composed of diamines with more than 6 carbons may contain an effective amount of non-aromatic Family diacids, as discussed above, are aromatic polyamidoamines based on 6 carbon diamines. This effective amount of the diacid needs to be sufficient to bring the melting point down to the desired molding temperature range without unacceptably affecting the desired solvent resistance properties. Other non-limiting examples of warm thermoplastic materials include polyphenylene sulfide, liquid crystal polymers, and high temperature polyfluorene. Liquid crystal polymers are chemically based on linear polymers containing repeating linear aromatic rings. Due to the aromatic structure, these materials form a nematic fused state region with a 4-segment interval that can be detected by X-ray diffraction. Examples of such materials include copolymers of benzoic acid, or copolymers of ethylene glycol and linear aromatic disulfide compounds such as terephthalic acid or naphthalenedicarboxylic acid. Nanwen thermoplastic polyimide contains aromatic dianhydride and aromatic diamine. Suitable polyimides include those available from several sources. Example A copolymer of 1,4-benzyl monoamine and ι, 2,4,5-tetracarboxylic dianhydride. In a preferred embodiment, the matrix comprises at least one fluorothermoplastic material. The thermoplastic fluoropolymers of SITA include those selected from a wide range of polymers and products. The polymer is preferably processed, so that it is thermally inactivated and maneuverable 'and can be easily processed by thermoplastic techniques such as injection molding, extrusion 21 200535005 molding, compression molding, and blow molding. The material is preferably recyclable by melting and reprocessing. In various embodiments, the thermoplastic polymer is fully or partially fluorinated. Fully fluorinated thermoplastic polymers include copolymers of tetrafluoroethylene and perfluoroalkylethenyl. Perfluoroxyl is preferably one to six carbon atoms. Other examples of copolymers are PFA (copolymer of TFE and perfluoropropenyl vinyl ether) and MFA (copolymer of TFE and perfluoromethyl vinyl ether). Other examples of fully fluorinated thermoplastic polymers include copolymers of TFE and perfluoroolefins having 3 to 8 carbon atoms. Non-limiting examples include FEP (copolymer of TFE and hexafluoro 10 propylene). Partially fluorinated thermoplastic polymers include E-TFE (a copolymer of acetamidine and TFE), E-CTFE (a copolymer of ethylene and monochlorotrifluoroethylene), and pVDF (polyvinylidene fluoride). Several thermoplastic copolymers of vinylidene fluoride are also suitable for use in the thermoplastic polymers of the present invention. These include copolymers with perfluoroolefins, such as hexafluoro 15 propylene, and copolymers with monochlorotrifluoroethylene. In various embodiments, thermoplastic terpolymers are used. These terpolymers including TFE, HFP, and vinylidene fluoride include commercially available fluorothermoplastic materials. Suppliers include Dyneon (3M), Daikin, Asahi Glass Fluoroplastics, Solvay / Ausimont and DuPont. In some commercial 20 examples, the partially fluorinated fluoroplastic has about 59 to about 76 weight percent fluorine. Useful curing agents include mixtures of diamines, peroxides, and polyol phosphonium salts. Diamine curing agents are relatively slow-curing, but offer advantages in several areas. Such curing agents are commercially available, for example, Diak-1 from DuPont Dow Elastomers. 22 200535005 A preferred peroxide curing agent comprises an organic peroxide, and is preferably a difluorinated peroxide. Preferably, the organic peroxide is selected as a curing agent in the presence of other ingredients and at the temperature of the soil to be cured during the curing operation and during the mixing or curing operation without causing any harmful amount. 5 is a curing agent for the composition. Dialkyl peroxides that decompose at temperatures above about 49 ° C are particularly preferred when the composition is subjected to processing at elevated temperatures before curing. In many cases, it is preferred to use a second tertiary butyl peroxide having a tertiary carbon atom attached to the oxygen of the peroxy group. Non-limiting examples include 2,5-difluorenyl · 2,5-di (third butylperoxy) _3_hexyne; 2,5_dimethyl1〇_2,5_di (third butyl Peroxy) hexane; and 1,3-bis-tert-butylperoxyisopropyl) benzene. Other non-limiting examples of peroxide curing agents include dicumyl peroxide, diphenylfluorenyl peroxide, third butyl perbenzoate, di [1,3-dimethyl-3- (Third butylperoxy) butyl] carbonate and the like. In various embodiments, one or more cross-linking co-reagents are mixed with the peroxide. Examples include triallyl cyanurate; tris (methallyl isocyanurate); tris (diallylamine) -s-triamidine, triallyl phosphite; n, n_ a Diluted propyl allyl amine, hexa fine propyl dish with amine; n, N, N, N, -tetradipropyl p-xylylenediamine; Amines; trivinyl isopropanoic acid, succinic acid, 2,4,6-diethylene methyl, three-second oxygen burning; and dinorylene, 20 tablets of alkenyl-2-methylene) cyanurate. Suitable iron salts are described, for example, in U.S. Patent Nos. 4,233,421, 4,912,171; and 5,262,490. Examples include triphenylbenzyl squall chloride, tributylxanthyl squidyl chloride, tributyl benzyl chloride, tetrabutyl beryllium desert, and triaryl chloride. 23 200535005 Another useful type of osmium salt is represented by the following chemical formula: jealous—〇— 《《霞霞 *} 奶

. ^ I where Q is nitrogen or phosphorus; 5 Z is a hydrogen atom, or a substituted or unsubstituted, cyclic or acyclic alkyl group having 4 to about 20 carbon atoms terminated by a COOA group of chemical formula Among them, A is a hydrogen atom or NH4 + cation, or Z is a chemical formula of CY2 COOR, a group of which γ is a chlorine or halogen atom, or a substituted or unsubstituted 10- to 6-carbon atom. Alkyl or aryl, which may optionally contain one or more quaternary heteroatoms, and wherein R1 is a hydrogen atom, a Nil / cation, an alkyl group, or an acyclic anhydride, for example, the chemical formula—COR group, Among them, R is an alkyl group or a group containing organic fluorene (that is, a bi-organic fluorene); preferably, R is a fluorene; z may also have 4 to about 20 carbons terminated by a chemical formula-COOA group. The atom is 15-generation or unsubstituted, cyclic or non-cyclic alkyl group, in which A is a hydrogen atom or NH4 + cation;

Each of Ri, R2, and R3 is a hydrogen atom or an alkyl, aryl, alkenyl, or any combination thereof. Each of Ri, r2, and r3 may be chlorine, fluorine, bromine, cyano, or -OR. ", Or -COOR" substitution, wherein R, is CjC20 alkyl, aryl, aryl, or fluorenyl, and any one of Ri, R2, and R.3 groups may be each other and Q Linked to form a heterocyclic ring; Ri, r2, and one or more of the heart group 24 200535005 may also be a group of the chemical formula Z, where Z is as defined above; X is an organic or inorganic anion (not limited For example, halides, sulfates, acetates, phosphates, hydroxides, alkoxides, phenoxides, bisphenoxides); and 5 η is a value equal to the anion X valence. The polymeric cross-linking agent can be any of these polyhydroxy compounds used as a cross-linking agent or co-curing agent for fluoroelastomers in this technology, such as disclosed in US Patent No. 4,259,463 (Moggi et al.), Polyhydroxy compounds of U.S. Pat. No. 3,876,654 (Pattison), U.S. Pat. No. 4,233,421 (Worm), and U.S. Defense Bulletin τ 丨 07,8〇 丨 (Nersasian). Preferred polyols include aromatic polyhydroxy compounds, aliphatic polyhydroxy compounds, and phenol resins. Representative aromatic polymer compounds include any of the following: di-, tri-, and tetrahydroxybenzene, naphthalene, and-onion, and bisphenol of the following chemical formula:

15 wherein 'A is a bifunctional aliphatic, cycloaliphatic, or aromatic group of 1 to 13 carbon atoms, or a thio group, an oxy group, a carbonyl group, or a sulfonyl group, and A is optionally Gas atom substitution, X is 0 or 1, η is 1 or 2, and any aromatic ring system of the compound is selectively substituted with at least one atom of a gas, fluorine or bromine atom, or a carboxyl group or a fluorenyl group (for example, --COR, wherein R is Η or (^ to (: 8 alkyl, aryl, or cycloalkyl) or an alkyl substitution having, for example, 1 to 8 carbon atoms. Known from the above formula of bisphenol— The oxo group can be attached to any position of 25 200535005 (not number 1). Blends of two or more of these compounds can also be used. The preferred bisphenol compound is bisphenol AF, which is 2 2,2-bis (4-hydroxyphenyl) hexafluoropropane. Other non-limiting examples include 4,4'-dihydroxydiphenyl stone (Sulfur S), and 2,2-bis (4-hydroxyphenyl) ) Propane (Bisphenol A). Aromatic poly5-based compounds such as hydroquinone can also be used as curing agents. Further non-limiting examples include catechol, resorcinol, 2-methyl Resorcinol, 5-methylresorcin, 2-methylhydroquinone, 2,5-dimethylhydroquinone, and 2-tert-butylhydrogen, 1,5--per-naphthalene, and 9 10- diacryl anthracene. Aliphatic polyhydroxy compounds can also be used as polyol curing agents. Examples include 10-fluoroaliphatic diols, such as 1,1,6,6-tetrahydrooctafluorohexanediol, And others such as those described in U.S. Patent No. 4,358,559 (Holcomb et al.) And references cited therein. Polyhydroxy compound derivatives can also be used, such as those described in U.S. Patent No. 4,446,270 (Guenthner et al.) And including, for example, 2- (4 · allyloxyphenyl) -2- (4-merylphenyl) propane. Mixtures of two or more polylight-based compounds can also be used. Phenolic resins of crosslinked rubber polymers can be used as polyol curing agents. Polyol resins can include mixtures of these resins. These resins are disclosed in U.S. Patent Nos. 2,972,600 and 3,287,440. These phenolic resins can be used for The desired degree of curing is achieved without the use of other curing agents. 20 Phenol resin curing agents Substituted phenol and aldehyde (preferably formaldehyde) are subjected to condensation reaction in an alkaline medium or obtained by condensation reaction of a bifunctional phenol diol. The alkyl substituent of an alkyl-substituted phenol typically contains 1 To about 10 carbon atoms. Dimethyl alcohol phenol or phenolic resin (substituted by an alkyl group containing 1 to about 10 carbon atoms at the para position) is preferred. There are 26 200535005 commercially available resins that include a sintered group. Phenol-formaldehyde resin and bromomethylated phenol-formaldehyde resin. In one embodiment, the phenol resin curing agent is represented by the following general formula:

5 wherein Q is a divalent group selected from the group consisting of -CH2- and -CH2-0 ~ ch2; m is a positive integer of 0 or 1 to 20, and R is hydrogen or an organic group. Preferably, Q is a divalent group -CH2-0-CH2-, m is a positive integer of 0 or 1 to 10, and R, is hydrogen or an organic group having less than 20 carbon atoms. In another embodiment, preferably, m is a positive integer of 0 or 1 to 5, and R is an organic group having 4 and 12 carbon atoms. Other preferred phenol resins are also disclosed in U.S. Patent No. 5,952,425. In addition to the elastomer material, the thermoplastic polymer material, and the curing agent, the processable rubber composition of the present invention optionally contains other additives, such as a 'stabilizer, processing aid, curing accelerator, filler, colorant, Adhesives, thickeners, and waxes. A wide variety of processing aids can be used in various embodiments, including plasticizers and release agents. Non-limiting examples of processing aids include Caranuba (R), acetic acid S plasticizers, such as dioctylacetate g (DO) and dibutyl phthalate silicate (DBS), fatty acids Salts such as zinc stearate 20 and sodium stearate, polyethylene wax, and keramide. In some embodiments, high temperature processing aids are preferred. These include, without limitation, linear 27 200535005 fatty alcohols, such as blends of Ci0-c28 alcohols, organolithones, and functionalized full gas poly bonds. In some embodiments, the composition contains about 1 to about 15% by weight of a processing aid, preferably about 5 to about 10% by weight. In various examples, the acid-acceptor compound is used as a curing accelerator or a preferred chelate-accepting compound. The acid-acceptor compound includes an oxide and a hydroxide of a divalent metal. Non-limiting examples include Ca (OH) 2, MgO, Ca0, and ZnO. Non-limiting examples of fillers include organic and inorganic fillers such as barium carbonate, zinc sulfide, carbon black, stone spar, titanium dioxide, clay, talc, 10 glass fibers, fuming stone, and discontinuous fibers such as , Mineral fiber, lignocellulosic fiber, Qianwei, Erwei, and aromatic __). Some non-limiting examples of processing additives include stearic and lauric acid. Carbon black, extender oil, or both (preferably on dynamic vulcanization) are particularly preferred. Non-limiting examples of slave black fillers include saf black, ME black, 15 SRP black, and Austin black. Carbon Black improves tensile strength, and the extender / improves processing properties, resistance to oil swelling, thermal stability, hysteresis, cost, and permanent set. In a preferred embodiment, such as the Weiji resist The fillers form up to about 40 weight 0/0 of the total weight of the composition of the present invention. Preferably, the composition contains about 1 to about 40% by weight of fillers. 10 to about 25% by weight. Acryl elastomeric materials are also commonly referred to herein as "rubbers," which are preferably present as small particles within a continuous thermoplastic polymer matrix. In some embodiments, they have a common success The morphology is based on the elastomeric material system and the curing mechanism and the degree and mixing content of the elastomer material relative to the thermoplastic material. The range is 28 200535005 degrees. Fully crosslinked / cured. Modification can be achieved by adding a suitable curing agent or curing system to the blend of thermoplastic materials and elastomeric materials, and sulphurizing or curing the rubber to the desired degree under curing conditions. The elastic system in the dynamic vulcanization method and the external ear movement claw is a method for vulcanizing or curing the rubber contained in the thermoplastic composition (in this case, a carbon-deficient compound elastomer), wherein the curable rubber is A temperature higher than the melting point of the thermoplastic component and vulcanized under sufficiently high shear conditions. The rubber is therefore simultaneously crosslinked and dispersed in the thermoplastic matrix 10. The vulcanization of vulcanizates is traditional by increasing the temperature and in the presence of the curing agent. Mechanical energy is applied in mixing equipment (such as drum mixers, MGriyama mixers, Banbury mixers, Brabender mixers, continuous mixers, hybrid extruders, such as' single and twin screw extrusions ||, etc.) Elastomer and thermoplastic components are mixed. The dynamic curing of the composition is beneficial. 15 series, even after 70 full curing, the composition can be processed by traditional plastic processing techniques (such as extrusion, (Extrusion molding and compression molding) processing and reprocessing. Broken genus or scintillators are preferably used and reprocessed by waste. Heating and mixing or grinding at vulcanization temperature is preferably within 20 or less minutes. The vulcanization reaction is completed, but if a shorter vulcanization time is required, higher temperatures and / or higher shear can be used. A suitable range of vulcanization temperature is about the melting temperature of the thermoplastic material (typically about 20 °). 〇 to about 300% or more. Typically, this range is about 150. (: to about 250 ° c. The preferred range of vulcanization temperature is about 180 ° C to about 220 ° C. Preferably, the mixing system is间 所 29 200535005 until vulcanization continues or occurs completely. The processable rubber composition of the present invention can be manufactured in a batch or continuous manner. In the batch method, a predetermined amount of elastomeric material, thermoplastic material and curing agent are added to the mixing device. In a typical batch process, the elastomeric material and the thermoplastic material are first mixed, blended, ground or otherwise physically mixed to the desired particle size. The elastomeric material is provided in a continuous phase thermoplastic material. When the structure of the elastomeric material is as desired, a curing agent can be added while continuously applying mechanical energy to mix the elastomeric material and the thermoplastic material. Partial curing occurs by heating or continuously heating a mixture of thermoplastic and elastomeric materials in the presence of a curing agent, which takes less time than required to fully cure the elastomer. Preferably, the elastomeric material and the thermoplastic material are mixed at a temperature at which the thermoplastic material softens and flows. If this temperature is lower than the temperature at which the curing agent is activated, the dextrinizing agent may be a part of the mixed I5 material during the initial particle dispersion step of the batch method. In some embodiments, the curing agent is mixed with the elastomer and polymer material at a temperature below the curing temperature. When the desired dispersion is achieved, the temperature can be increased to produce curing. In one embodiment, a commercially available elastomeric material is used, which contains a curing agent pre-formulated in the elastomer. However, if the curing agent is activated at the initial mixing temperature, it is preferred that the desired particle size distribution of the elastomeric material leaving the curing agent in the thermoplastic matrix is achieved. In another embodiment, the curing agent is added after the elastomer and the thermoplastic material are mixed. In a preferred embodiment, the curing agent is a mixture of elastomer particles added to the thermoplastic material while the entire mixture is mechanically stirred, agitated, or otherwise mixed. 30 200535005 Continuous methods can also be used. In one embodiment, the twin-screw extruder device (with the same direction _ Qianxiang_ transfer material) may be provided with an orifice for material addition and a reaction chamber of a module assembly constituting the twin-screw device. A method for adhering a thermoplastic fluorocarbon elastomer composition to a substrate using a twin-screw extruder having a first orifice and a second downstream orifice. The method includes: ⑷ uncured fluorocarbon The mixture of the compound elastomer and the thermoplastic material is fed into the first orifice of the extruder, wherein the characteristic of the uncured body is T90 time; ⑻ the curing agent for the fluorocarbon elastomer is fed to the The second orifice is within the first orifice; the curing agent, the fluorocarbon elastomer, and the thermoplastic material are mixed in the dragon ΓΓΓ mold for a time or less to prepare a partially cured thermoplastic vulcanizate of the fluorocarbon elastomer. ; 15 20 热 Renew Viewpoint rubber converted from the extruded part; 涂敷 The thermoplastic vulcanizate is applied to the substrate; and (f) the cure of the heat count cured rubber on the substrate is complete. In the-embodiment, the thermoplastic material and the elastomer material (presenting the cured fat or glue) make the closing device (weightless type and volumeless type) from the first embedded screw extruded. The temperature and screw parameters are preferably adjusted to the appropriate temperature and shear size for the unmixed body components to be mixed and the particle size distribution in the thermoplastic. The longer or shorter length of the extrusion is set or controlled. Used to make the bomb: the speed of rotation of the screw through which the bulk material and the thermoplastic material pass during the mixed phase is controlled by 31 200535005. The degree of mixing can also be controlled by the structure of the mixing helical element of the screw shaft, such as a cesium set, a moderate or mild spiral design. Then, in the downstream hole: By using a side feeder (weightless or volumeless feeder), the curing agent can be continuously added to 5 thermoplastics as it continues downward through the twin-screw extrusion path. A mixture of materials and elastomeric materials. The% parameters and the passing time of the orifice added to the curing agent can be changed as described above. By adjusting the shear: speed, temperature, mixing period, mixing screw element structure, and adding curing N 'between the' partially cured dynamic vulcanizate of the present invention can be prepared by a continuous 102 method. As with the batch method, the elastomeric material can be commercially formulated as a curing agent, typically a phenol or phenol resin curing agent. —The composition and article of the present invention will contain a sufficient amount of vulcanized elasticity = material ("rubber") to form a rubbery material composition, that is, it will exhibit the properties of flexibility, flexibility, and compression. To be mixed. Preferably, the composition needs to contain at least about 25 15 ^ parts of rubber, preferably at least about 35 parts by weight, and more preferably at least 15 parts by weight of rubber and thermoplastic polymer. 40 parts by weight of rubber, more preferably at least about 45 parts by weight of rubber, and more preferably at least about 5G parts by weight of rubber. The amount of curing in a thermoplastic vulcanizate is generally the total weight of the rubber and thermoplastic polymer mixed It is about 95% by weight, preferably about 35% by weight, more preferably about 35% by weight, more preferably about 20% by weight, about 90% by weight, and still more preferably by about 50% by weight and about 80% by weight. The thermoplastic polymer in the rubber composition which can be processed is generally about 5 to about ri / 0 of the total weight of the mixed rubber and thermoplastic material, preferably about 10 to about 65 weight 〇 / 〇, and more preferably It is about 20 to about 50% by weight. 32 200535005 The present invention The rubber composition that can be processed in the composite includes two-part rubber and thermoplastic polymer. The composition is a homogeneous mixture. The rubber is finely divided and fully distributed in the unvulcanized substrate. However, it should be understood that the thermoplastic vulcanizate of the present invention is not limited to those containing a discontinuous phase, because the composition of the present invention may also contain other forms, such as a common continuous form. In a particularly preferred embodiment, the rubber particles have less than about 5 The average particle size of 〇11111 is more preferably less than about 25 μηι, more preferably less than about 10 Km or less, and more preferably less than about 5 μιη. The fully cured material is rubber-like until it is at room temperature It is stretched to its original σ length by two points and if released for 1 minute, it will retract to at least 1.5 times its original length within 1 minute, as defined by astm D1566. Furthermore, these materials satisfy The requirements for tensile strain resistance shown in ASTM Ό412, and it also meets the elastic requirements for compression set through ASTM D395. The composite article is made of a rubber composition as described above attached to a substrate 15%. The adhesive layer can be provided on the substrate in contact with the partially cured thermoplastic vulcanized rubber knee as described above. The adhesive layer is made of a fluoroelastomer material suitable for bonding to a metal, plastic or ceramic. The adhesive composition on the substrate is made. In general, the adhesive layer will contain a coupling agent that easily reacts with one or two surfaces to be joined and increases the bonding strength. These coupling agents generally have chemical properties of 20 degrees. One interacts with the surface of the substrate, and the other interacts with the fluoroelastomer component of the bonding interface. The coupling agent can be represented by the structural formula "RMY", where R is the base that reacts or interacts with the polymer, and Y is a base that reacts or interacts with metals, plastics, or ceramics or other materials that make up this substrate. In the case where the substrate contains gold 33 200535005, the γ group is generally a hydrolysis-sensitive type. The γ group is easily removed under acidic or experimental conditions to produce a more reactive mesial functional group. An example of such a coupling agent is a commercially available second firing. Silane has the general formula R-Si- (0R,) 3, wherein R is as defined above, and 5 R- is methyl, ethyl or lower alkyl. Appropriate groups include ethylene, aminopropyl, methacryloxy, weyl, and glycidyloxy. Non-limiting examples of silane coupling agents used in the adhesive composition are vinyl triethoxylate and 7-aminopropylite. In one aspect, commercially available adhesives for bonding carbohydrate elastomers to metals and other substrates can be used, and their activity and efficacy are promoted by practicing the method of the present invention. The uncured rubber or elastomer is preferably provided in the form of a resin or glue having little or no elastomeric properties. The resin or glue is preferably cured or conjugated to provide materials having advantageous properties such as flexibility, softness, elasticity, compression set and the like. This curing is performed at a selected temperature until the physical properties of the elastomer are fully developed. During curing, the physical properties gradually change from the non-elastomeric properties of the gum or resin to the elastomeric properties of the fully cured resin. A convenient way to follow curing development is to measure the viscosity of a material as a function of time. A cured rubber system is characterized by an increase in viscosity from the beginning of curing to completion. 20 In one aspect, the bonding between the fluorocarbon elastomer material and the solid substrate is performed by applying a partially cured fluorocarbon elastomer composition to the substrate and making the curing completely when the two are in contact. promote. Experimentally, this can be done by dynamically curing the fluorocarbon elastomer composition in less time than required to fully develop its elastomer properties. For example, fluorocarbon bomb 34 200535005 can be cured for less than or equal to T% of time, where τ90 is based on the reaction temperature during which the viscosity of the reaction mixture increases by 90/0 will achieve complete curing It depends on the rubber time. In a preferred embodiment, the fluorocarbon elastomer composition is cured in less than T90, such as 5 T90 minus 30 seconds, or T90 minus 60 seconds. In this partially cured state, the material can be extruded or molded, but complete elastomeric properties are not developed until further curing time. Curing parameters such as T90 can be determined in individual experiments by curing the fluorocarbon elastomer component of the thermoplastic vulcanizate of the present invention. The average viscosity of 10 degrees is based on RPA (Rubber Processing Analyzer). T90, Ts2, and other parameters can be determined conventionally. For the fluorocarbon elastomer material of the present invention, the T90 range at typical temperatures is less than 1 minute to several minutes, such as up to 2-5 minutes. Therefore, the curing time for the fluorocarbon elastomer component applied to the substrate to become partially cured is generally relatively short. In this case, it means that it will be easier to experimentally perform partial curing and coating to the substrate by the continuous or semi-continuous method described below. The curing time for a system with double-strength curing (no post-curing or low post-curing) is on the order of 2-5 minutes as described above. The system cured with peroxide is easy, and there is a low T90 in the car. Typically, less than 1 minute is used for peroxide-cured systems. Generally, the partially cured thermoplastic vulcanizates of the present invention are prepared according to a general process for manufacturing dynamic vulcanizates of rubber and thermoplastic materials. In particular, these methods are similar to those disclosed in the related application US Serial No. 20,213. The difference is that the curing is performed in a short time to achieve partial curing. 35 200535005 Thermoplastic vulcanizate synthesis. In the batch method, the elastomer, thermoplastic material and curing agent are mixed together in a mixer, and the partially cured material is collected for later use. Continuous or semi-continuous methods can be implemented in a twin-screw extruder, during which the mixing time is determined by the mixing rate and the sleeve length by 5 degrees. The partially cured thermoplastic vulcanizate can be extruded from a twin-screw extruder through a standard mold, cooled in a water bath, and cut into pellets for later use. In addition, the partially cured thermoplastic vulcanizate can be extruded from a twin-screw extruder into a co-molded mold or an inset mold rain for application to a substrate. 10 15 20 After the partially cured thermoplastic vulcanizate is applied to the substrate, the curing of the partially cured elastomer composition of the elastomer is completed when the elastomer composition is in contact with the substrate. This can be accomplished by further curing when the co-extruded or insert-molded substrate / elastomer composite is exposed to elevated temperatures after coating. In the case of insert molding, the composite article can be maintained in a mold at elevated temperature for a time sufficient to complete curing. For the limb of a co-extruded object (such as an m-hose), this branch can provide the co-extruded product at a time and temperature sufficient to fully immortalize and fully contact with the substrate simultaneously, 2. The coupling agent in the Lu adhesive layer interacts or touches its effect to cause the promoted bonding effect. ^ The present invention is shown in the following pure examples. The following examples are shown. Tian'L Example 1 Elastomer and reaction during curing. It is believed that this interaction is further non-limiting. T90 is measured by RPA (curing of various fluorocarbon elastomers 36 200535005 rubber processing analyzer). For Dyneon (R) BRE 7231X, a bisphenol curable terpolymer elastomer, T90 was measured to be 124 seconds. For Tecmoflon® FOR80HS, no (low) post-curing bisphenol curable terpolymer elastomer, T90 is measured for 217 seconds. TeCnOflOnP457, a peroxide-curable terpolymer elastomer, has a T90 measured for 26 seconds, and a Tecnoflon P757 measured T47 for 47 seconds. Dyneon materials are available from 3M, and Tecnofkm materials are available from Solvay. Blanket 2-More than compound cured curable elastomers. The process of producing partially cured 10 FMK-TP V with peroxide curable FKM elastomers is as follows: Make fluorocarbons. Elastomers and plastics are melted in a batch mixer at an elevated temperature (120 ~ 200 (&c; c). Those whose temperature is lower than the FKM-TPV dominated by bisphenol-curable FKM are due to Low degradation temperature of oxide curing agent (generally 80 ~ 200 °). Filler, curing agent packaging and processing aid 15 are added to the batch mixture. Continue mixing until homogeneous mixing and partial curing are achieved. Up to thermoplastic vulcanizate (TPV) (generally a mixing time of 1-3 minutes with a 50RPM rotor speed. The mixing time is determined by the T90 curing time. For a typical peroxide curable elastomer K18 (rc time series) 30 ～ 90 seconds. The curing time is also determined by the type of peroxide curing agent (Ti / 2).%. The di 1/2 of the leg i ^ 20 is 1820C, and the T1 / 2 of PerkadoxTML is 80. T. Mixing time can be extended by using a lower temperature than T1 / 2, because at lower temperatures The reason for the lower solidification rate is to manufacture batch-processed TPVs, mainly silanes, with adhesive-coated metal abrasive slabs for injection molding or extrusion molding of shells for embedded mold operations. The adhesive layer can be sprayed, or the shell can be impregnated or immersed in the adhesive. The metal shell coated with the adhesive is embedded in the mold. The shell is preheated in the furnace to 100-250. 0 injection The molding machine is heated to melt the TPV at 120-200 ° C. The TPV material is injected (2000-3000 psi injection pressure) onto a metal shell coated with an adhesive and under pressure (800-1500 psi) Hold it together for 5-180 seconds to contact the adhesive layer and the molten Tpv material together and react to promote the bonding layer. The nucleated sample is released from the mold and immediately or after a short post-heat treatment (for example, in 1 hour in a 230 ° C furnace) Evaluation of bonding characteristics. 10 15 20 After the peel test, the damaged area was inspected by SEM and EDAX, and the failure mode was evaluated by individual scanning images and elemental analysis by χ · ray. . For example, the scanned SEM image can be associated with each individual element ( (Fe), silicon fluorene), _), phosphorus (P), etc.), such as: 乂 Bisphenol-curable FKM (normal and no post-curing) The procedure for manufacturing partially cured FMK-TPV is as follows Indication: Fluorocarbon, sex body and thermoplastic materials are blended in the batch mixture with heart-lifting degree of '22G ~ 25G ° c). Filler, curing agent packaging-human assistant is added to the batch mixture. Continue mixing until A homogeneous mixture is obtained and the rate of partial curing (a fine butterfly). = / τ 料 止 ⑻0, the rotor depends on the typical double W of ^ = τ5_㈣, its pair FKM ^ -A-, ', ~ 5y knife clock. For example, for a typical T9G post-cured T-body, it is 2.3 minutes, and for a typical elastomer, _, 3.4 minutes. Grinding thick blocks of FKM-TPV 38 200535005 processed for injection molding or extrusion processing. An adhesive-coated metal shell was prepared as in Example 2. The TPV and the case were insert-molded as in Example 2. Samples that have not been prepared are tested for bonding behavior immediately after they are released from the mold and immediately or after a short post-heating treatment (generally within 22 hours within 23 °). For non-post-curing additives, use heat treatment after about 1 hour. Example 4-Continuous process Alpha-cure thermoplastic vulcanizates can be produced in a continuous process in a twin-screw extruder. 10 Mill the fluorocarbon elastomer to the size of the thermoplastic particles. The ground elastomer is mixed with thermoplastic pellets. The mixture of ground elastomer and thermoplastic pellets is poured into the feeder of a twin screw extruder. Set the screw sleeve temperature above the melting point of the thermoplastic (for example, about 200-280 ° C). Start feeding the mixture of elastomer and thermoplastic material into a heated 15 sleeve. When the screw is rotated to push the mixture to the front of the twin-screw extruder, the elastomer and thermoplastic material are melted, compressed, and mixed. Add the curing agent, curing acceleration back J, processing aid and carbon west mixture through the side feeder of the downstream feeding station. This mixture of elastomer and thermoplastic material needs to be completely melted and homogeneously mixed 20 before adding the powder mixture (for example, 5-10 minutes at 200 rPm and 240 ° C). Elastomers, thermoplastic materials, curing agents, curing accelerators and other additives are mixed in the sleeve of the twin-screw extruder downstream of the side feeder. The mixed σ-day interval is determined by the screw speed and sleeve length. The mixing time needs to be T90 or less. Among them, Ding 90 is the curing parameter of the elastomer. 39 200535005 The partially cured thermoplastic vulcanizate is discharged through the wire mold at the end of the sleeve of the twin-screw extruder. The extruded material is passed through a water bath for cooling, and cut into appropriate lengths to provide pellets for subsequent processing steps. For bisphenol curable elastomers, it is typically used for about 2 minutes in the extruder sleeve before curing agent 5 is added. A typical screw speed is 200 rpm at a set temperature of about 240 C. The retention in the sleeve after the remaining components are added via the downstream feeder is typically less than 30 seconds. After being extruded from the wire mold, the extrudate is preferably quenched or rapidly cooled by a cooling water bath. For peroxide-curable elastomers, elastomers and thermoplastics 10 are mixed in an extruder sleeve at a screw speed of 200 rpm and a sleeve temperature of 150 ° C for about 2 minutes before the curing agent is added. These parameters are similar to those used for bisphenol-curable elastomers, but the sleeve temperature is generally slightly lower. Typically, the residence time in the sleeve after adding the curing agent package is less than 30 seconds. The curing agent package may be added as the pellets 15 in a powder type or a master batch type. A typical T90 cure time for peroxide-curable elastomers is 30-90 seconds at 180 ° C. The T90 time can be extended by lower temperature curing. For example, at a compounding temperature of 15 ° C, a typical T90 curing time is about

2-3 minutes. As mentioned above, the 'extruded material is preferably quenched or rapidly cooled in a cooling water bath after being extruded from a wire mold. V 20 Example 5-Multi-layer coextrusion 裎 Several screw extruders (for example, 2-5 extruders; in some embodiments, 3 extruders) are connected to a multi-die mold. For water-based adhesives: the tie layer extruder can be replaced by a continuous liquid injection unit. The sleeve of the extruder for each of the layer materials is heated. Partial curing 40 200535005 ... plastic | ± vulcanized rubber extruder typical temperature is 24o. The typical temperature of a thermoplastic elastomer substrate based on resistance theory (such as pebax⑧403) is 200 ° C. At the same time, the inner layer extruder and the outer layer extruder, including the continuous injection unit of the adhesive ^ layer extrusion 1§ The wire is quenched in a cooling water bath when it leaves the coextrusion die. Typically, the size of a single screw extruder is about 1-2 inches in diameter, and the rate of the screw is 20-100 rpm. The size and speed of the screw depend on the thickness of each layer and the rate of coextrusion. 10. The products produced by co-extrusion can be of the sheet type, or the types of concentric extrusion products (such as Liguan). After co-extrusion, the curing of the partially cured thermoplastic vulcanizate is completed at elevated temperatures. The coextruded composite article contains a fully cured fluorocarbon elastomer thermoplastic component bonded to an elastomer or plastic substrate. When a composite object is formed by concentric co-extrusion, such as m soft 15 tube, the typical structure of the cured fluorocarbon elastomer composition is the inner layer of the hose, and the elastomer or thermoplastic material forms the outer layer of the hose. For sheet composite objects that are concentric, a tie layer can be provided between the fluorocarbon elastomer and the substrate. Non-limiting examples of elastomers that can be used as substrates include

EPDM, NBR, HNBR, ACM, AEM, FKM, PU, FFKM 20 and silicone elastomer. Non-limiting examples of thermoplastic materials that can be used as substrates include polystyrene, carbon fiber, polyvinyl acetate, PVC, fluoroplastics, and plastic elastomers (such as' available from Hytrel®, Pebax®, Santoprene®, Pellethane®, and Kraton® is a commercially available thermoplastic polyurethane and thermoplastic elastomer). The connecting layer is made of an adhesive that can join a cured fluorocarbon elastomer composition 200535005 and an elastomer / thermoplastic material layer. Adhesive compositions based on Wei or maleic anhydride are commercially available for this purpose. The single-screw extruder, which supplies the partially cured thermoplastic vulcanizate to a common extrusion mold, is provided as a double-sleeve twin-screw extruder that can also be used directly to produce thermoplastic sulfur rubber in a continuous process. If desired, the output of the twin-screw extruder can be directly used as the input to the multi-layer extrusion die of a co-extrusion device without the need to cool the partially cured thermoplastic vulcanizate wire in a water bath. The pelletizing, remelting, and reextrusion steps can be removed by connecting the compounding extruder to a multilayer extrusion device. 10 Preferred Example 6-Combination of fluorocarbon elastomer composition and metal substrate Example 6A-Joining of partially cured peroxide curable elastomer The following ingredients were used: 80 parts Tecnoflon P757 (available from Solvay Peroxide curable fluoroelastomer); 25 parts of Kynar Flex 2500-04 (a thermoplastic material based on vinylidene fluoride from 15 Atofina Chemicals); 5 parts of zinc oxide; 10 parts of carbon black; and 20 parts of Masterbatch. Mix the Tecnoflon P757 and Kynar Flex 2500-04 at 15 ° C for 5 minutes while mixing to form a homogeneous mixture. Add zinc oxide. Add the master batch to the batch mixer and mix for 30 seconds (master batch system Prepared by mixing 20 100 parts of Tecnoflon P757, 15 parts of Luperco 101 XL, and 20 parts of 75% TAIC dispersion in an individual batch mixer at 80 ° C. The mixture is discharged from the batch mixer, Cool and cut it into small particles or pellets with a size of about 1-3mm. Pour these pellets into the feeding port of the molding machine. Heat the injection molding sleeve to 150QC. According to the manufacturer's instructions Commercially available silane-based adhesives 42 200535005 Coated metal substrates (such as the case for sealing materials, the adhesive-coated case is embedded in the mold, and the molten mixture is injected on the metal case. Peripherals can be Preheat in a furnace at about 200 ° C, or it can be heated in the mold before injection. This preheat easily improves the adhesion between the adhesive layer and the fluorocarbon thermoplastic vulcanizate. After injection, the mold is under pressure (800 -1500 psi) maintained together for 1-2 During this time, the material was completely cured. Example 6B-Comparative Example Example 6B was implemented as in Example 6A, but the masterbatch, zinc oxide, Tecnoflon, and Kynar materials were mixed for 3-5 minutes instead of 30 seconds. 10 Example 7 Example 7A-The bonding with a partially cured bisphenol curable elastomer is 100 parts Tecnoflon for 80HS (a bisphenol curable fluorocarbon elastomer from Solvay, and Phenol curing agent is formulated in 15 resins); 25 parts Hylar MP-10 (fluoroplastic from Solvay); 3 parts magnesium oxide; 30 parts carbon black; 1 part Struktol WS-280 (processing aid from Struktol Tecnoflon FPA-1 (high temperature processing aid from Solvay). Tecnoflon FOR 80HS and Hylar MP-10 were melted in a batch mixer at 190 ° C for 1 minute until the polymer was homogeneously mixed. Add The remaining 20 parts are stirred at 190 ° C for another minute to fully disperse. The mixture is discharged from the batch mixer, cooled, and cut into ^^ claw pellets. The cut mixture is poured into a molding feed. Material mouth. Heat the injection molding sleeve to 2400c. The coated metal shell is embedded in the mold, and the mixture is injection molded on the metal shell. The mold is preheated in the furnace or in the mold to about 43 200535005 25QC. After injection, the mold is continuously maintained at 80-1500 psi. It lasts 3-5 minutes together, during which the curing is completed. Example 7B-Comparative Example The procedure is the same as in Example 7A, but the mixing system is performed for 5-10 minutes, and 5 is substituted for 1 minute before the remaining components are added. Example 8 The procedure is the same as in Example 7A, but the components are 70 parts of Dyneon FE840 (cured polymer obtained from Ausimont) and 30 parts of Dyneon BRE 7231X (alkali-resistant elasticity from Dyneon). Body), 25 # Hylar 10 MP-10, 6 parts of Rhenofit CF (calcium hydroxide from Rhein Chemie), 3 parts of magnesium oxide, 1 part of Stmktol WS-280, 10 parts of carbon black, and 1 part of Tecnoflon fpa_i. For all of Examples 6-8, after the fluorocarbon elastomer composition was in contact with the substrate and was completely cured, the adhesion between the elastomer and the substrate was measured using a tensile tester 15 to measure the separation strength. Thereafter, the separated areas can be inspected to assess the failure mode. The failure areas of composite objects (Examples 6, 7A, and 8A) prepared by injecting a partially cured thermoplastic vulcanizate onto a substrate exhibited cohesive failure. This means that the elastomeric material itself is broken, not the bond between the elastomer and the substrate. This indicates a relatively high degree of adhesion and joint strength. On the other hand, the failure area of the composite piece (Examples 6B and 7B) prepared by injecting the fully cured elastomer showed joint failure. For fully cured cases, most elastomers are removed from the substrate during the tensile test. This indicates relatively weak adhesion or bonding strength because the failure mode is the bonding rather than the elastomeric material itself. This failure mode can be visually observed and confirmed with a microscope inspection (such as with a scanning electron microscope). Furthermore, the failure mode can be confirmed by measuring the element map of the composite object by EDAX after the tensile test. For example, the area where the elastomer is still attached to the surface of the substrate is characterized by a high fluorine content, while the substrate with an adhesive is characterized by a relatively high content of iron and silicon. Typically, the elemental map of the cohesive-damaged elastomeric layer shows high silicone content. Silicon migrates from the adhesive layer into the surface layer of the elastomer and promotes the adhesion between the elastomer and the adhesive layer at the interface.

I: Simple style description 3 (None) 10 [Description of main component symbols] (None)

45

Claims (1)

200535005 10. Scope of patent application: 1. A method for adhering a thermoplastic elastomer composition to a solid substrate, comprising: (a) Dynamically vulcanizing a fluoroelastomer in the presence of a thermoplastic material and a curing agent 5 for continuous curing for complete curing The fluoroelastomer takes less time to form a partially cured thermoplastic vulcanizate; (b) applies an adhesive layer to the substrate; (c) causes the partially cured thermoplastic vulcanizate and the adhesive layer Contact; and 10 (d) complete curing of the thermoplastic vulcanizate. 2. The method of claim 1, wherein element (c) of the method includes insert-molding a partially cured thermoplastic vulcanizate on the substrate covered with an adhesive. 3. The method of claim 2 in which the substrate is a metal. 15 4. The method of claim 1, wherein the substrate is plastic. 5. The method of claim 4 in which the element (c) of the method includes co-extruding a partially cured thermoplastic vulcanizate with the substrate. 6. The method according to item 5 of the scope of patent application, wherein the element (b) of the coating method and the element (c) of the method include the adhesive layer, the partially cured thermoplastic 20 rubber, and the base Materials are co-extruded. 7. The method of claim 6 in which the adhesive layer is applied during coextrusion in a liquid continuous injection unit. 8. The method of claim 1, wherein the curing agent comprises bisphenol. 9. The method of claim 1, wherein the curing agent comprises a peroxygen compound. 10. —A method of manufacturing a composite article, comprising: (a) applying a partially cured thermoplastic elastomer composition to a substrate, wherein the thermoplastic elastomer composition includes a partially cured portion of fluorine 5 Elastomer and continuous phase thermoplastic polymer materials; and (b) curing the partially cured thermoplastic elastomer composition. 11. The method of claim 10, wherein the partially cured thermoplastic elastomer composition comprises a partially cured dynamic vulcanizate of a fluoroelastomer and a thermoplastic material. 10 12. The method of claim 10, wherein the fluoroelastic system is a copolymer of vinylidene fluoride. 13. The method of claim 10, further comprising mixing the fluoroelastomer, the thermoplastic material, and the curing agent together and heating the fluoroelastomer in the presence of the thermoplastic material to partially cure the fluoroelastomer. Method 15 forms the partially cured thermoplastic elastomer composition. 14. The method of claim 13 in which the thermoplastic material includes a fluoroplastic. 15. The method of claim 13 in which the thermoplastic material contains a fluorine-free thermoplastic material. 20 16. The method of claim 13 in which the thermoplastic material comprises a partially fluorinated thermoplastic material. 17. The method of claim 13 in which the curing agent comprises double hope. 18. The method according to item 13 of the patent application, wherein the curing agent contains 47 200535005 oxide. 19. The method of claim 10, wherein the substrate comprises an adhesive layer on a solid support, and the partially cured composition is coated on the adhesive layer. 5 20. The method of claim 10, wherein the element (a) of the coating method includes loosely molding the partially cured composition on the substrate. 21-The method of claim 10 in the scope of patent application, wherein the element (a) of the coating method comprises co-extruding the partially cured composition and the substrate. 22. A method for manufacturing a polymer composite article, comprising: 10 (a) manufacturing a partially cured dynamic vulcanized rubber having a fluoroelastomer discontinuous phase and a thermoplastic material continuous phase; (b) dynamics of curing the portion The vulcanized rubber is co-extruded with the substrate; and (c) the curing of the partially-cured partially cured dynamic vulcanized rubber is completed. 15 23. The method according to item 22 of the patent application range, wherein the adhesive layer is co-extruded between the partially cured dynamic vulcanizate and the substrate. 24. The method of claim 22 in the patent scope, wherein the liquid adhesive is injected between the partially cured dynamic vulcanizate and the substrate during element (b) of the 忒 coextrusion method. 20 is a method according to item 22 of the scope of patent application, which comprises mixing a fluoroelastomer with a thermoplastic polymer material and a curing agent that reacts with the fluoroelastomer resin, and simultaneously heating to cause the The fluoroelastomer resin and the solid reaction method correspond to a T90 or less time of the fluoroelastomer to manufacture the partially cured dynamic vulcanizate. 48 200535005 26. The method of claim 25, wherein the fluoroelastomer resin contains uncured monomers selected from the group consisting of hexafluoropropylene, vinylidene fluoride, tetrafluoroethylene, and mixtures thereof. Copolymer. 27. The method according to claim 25, wherein the curing agent comprises double 28. The method according to claim 25, wherein the curing agent comprises peroxide. 29. A method for manufacturing a composite article of a cured fluoroelastomer composition contained on a solid metal substrate using a mold, the method comprising: (a) applying an adhesive layer to the substrate; (b) ) Place the substrate covered with the adhesive in the mold: ⑻ contact the partially cured body yarn m with the substrate in the mold; and (d) complete the curing of the elastomer composition 15 20 Huaren = The partially cured elastomer contains a discontinuous phase containing a partially cured carbon gas secretion and a continuous 30% fluorine-containing thermoplastic material. • If the scope of the patent application is the 29th fluoroelastomer Resin, __, human private law 'further includes the following steps: mixing the curing agent with the corresponding agent, and preparing the partially cured elastomer by a method of reacting with the fluoroelastomer resin. The heat causes the resin. And curing agent at curing time T90, and the solidified body, wherein the resin is characterized in that the reaction time is less than T90. 31. The rod extruder such as the 30th item in the patent scope is implemented. To go, where, the mixing is based on the method of Shuang 49 49350035005 I2 into the 3G method of the patent application, wherein the fluoroelastomer resin i3 is a copolymer of vinylidene fluoride, hexafluorodiene and tetrafluoroethylene. 33. The method according to claim 30, wherein the curing agent comprises a double hope. 34. The method according to claim 30, wherein the curing agent comprises a peroxide. A method for adhering a thermoplastic fluorocarbon elastomer composition to a substrate by using a twin-screw extruder having a first hole and a second downstream hole. The method includes: 10 15 20 The mixture of the compound and limb thermal material is fed to the first orifice of the extruder, wherein the uncured elastomer is characterized by T90 time; 固化 a curing agent for the fluorocarbon elastomer is fed to the The second orifice is within the first orifice; 混合 The curing agent, the fluorocarbon elastomer and the thermoplastic material are mixed in the extruder or less time to obtain a partially cured thermoplastic of the fluorocarbon elastomer Vulcanized rubber; 挤 extruding the partially cured thermoplastic vulcanizate from the extruder; (e) applying the thermoplastic vulcanizate to the substrate; and (f) completing the curing of the thermoplastic vulcanizate on the substrate. 36. The method of claim 35, wherein the main point of the coating method includes molding the partially cured thermoplastic vulcanizate in a mold containing the substrate. 37. The method according to item 35 of the patent application scope, which includes heat curing the part 50 200535005 Plastic vulcanizate and the substrate are co-extruded. 38. The method of claim 35, wherein the fluorocarbon elastomer comprises a copolymer of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene. 39. The method as claimed in claim 35, wherein the curing agent comprises double 5 10. 40. A method as claimed in claim 35, wherein the oxide. 41. The method according to item 35 of the patent application, which includes fluoroplastics. 42. The method according to item 35 of the patent application, which contains a partially fluorinated fluoroplastic. 43. The method of claim 35, which contains a fluorine-free thermoplastic material. The curing agent contains, the thermoplastic material package, the thermoplastic material package, and the thermoplastic material package. 51 200535005 7. Designated representative map: (1) The designated representative map in this case is: (). (None) (b) Brief description of the component symbols in this representative drawing: (none) 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: